CN1981927B - Cobalt-based Fischer-Tropasch synthetic catalyst and its production - Google Patents
Cobalt-based Fischer-Tropasch synthetic catalyst and its production Download PDFInfo
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Abstract
A Co-based Fischer-Tropsch catalyst contains Co and Al, and is prepared through mixing Co-contained compound, Al-contained compound and water to obtain a solution, burning the solution in oxygen contained atmosphere to obtain a powder, and calcining at 100-1000 deg.C for 0.5-36 hr in air. Another preparing process is also disclosed. It has higher activity and selectivity.
Description
Technical field
The present invention relates to a kind of fischer-tropsch synthetic catalyst and preparation method thereof, more specifically to a kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof.
Background technology
Fischer-Tropsch is synthetic to be meant that synthesis gas (mixture of carbon monoxide and hydrogen) changes into the reaction of hydrocarbon compound in the presence of catalyst.The catalyst that is suitable for Fischer-Tropsch synthesis is a lot, and these catalyst contain metal component and the inert carrier that is selected from the group VIII in the periodic table of elements usually.Wherein, Co based Fischer-Tropsch synthesis catalyst is because C
5 +The selectivity height is a catalyst commonly used during Fischer-Tropsch synthesizes.
In cobalt-base catalyst, introduce other promoter metal component and can further regulate and improve catalyst performance.For example: it is favourable to improving catalyst activity to introduce promoter metal component K, Na, Mg, Sr, Cu, Mo, Ta, W or other group VIII metal component, introduce Ru, Zr, rare earth oxide (REO) or Ti and can increase the selectivity of catalyst the macromolecule hydrocarbon, Ru, REO, Re, Hf, Ce, U or Th are to favourable (the Catalysis Today of the regenerability of improving catalyst, 23,1995,21-22).
CN 1087193C discloses a kind of cobalt and manganese and/or vanadium catalyst of containing, and points out when cobalt: (manganese+vanadium) be at least 12: 1, when preferably being at least 1500: 1, catalyst has higher C
5 +Selectivity and greater activity.
US 6,586, and 481 disclose cobalt-base catalyst, and this catalyst mainly is made up of the alumina support of cobalt oxide and inertia, and described cobalt oxide is that average grain diameter is
Crystalline solid.Point out that (wherein, cobalt oxide is that average grain diameter is to the catalyst for preparing with respect to conventional method
Crystalline solid), the distribution of cobalt on carrier improves, thereby the units activity (specificactivity) of the reactive metal in the catalyst is improved.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of new have more high reaction activity and optionally Co based Fischer-Tropsch synthesis catalyst and preparation method thereof are provided.
Catalyst provided by the invention contains the cobalt metal component and the aluminium oxide of effective dose, and the mole atomic ratio of cobalt wherein and aluminium is 1:＞3-60, and the RT value of described cobalt metal component is 400 ℃ to 1000 ℃; Described RT value is for adopting temperature programmed reduction (TPR) when catalyst is characterized, the summit temperature of the first reduction spectrum peak correspondence in the reduction spectrogram of the cobalt that exists with the oxidation state form.
The invention provides the Preparation of catalysts method comprises cobalt aluminate is mixed with aluminium oxide and/or aluminium oxide precursor and roasting, it is 1 that the consumption of each component makes the mole atomic ratio of cobalt and aluminium in the final catalyst:＞3-60, described sintering temperature is 100 ℃-1000 ℃, and roasting time is 0.5-36 hour.
The another kind of preparation method who the invention provides catalyst comprises: (1) mixes, is dissolved into solution with at least a aluminum contained compound, at least a cobalt compound and at least a organic cosolvent with water; (2) described solution is heated to burning, burn off organic cosolvent under oxygen-containing atmosphere, obtains a kind of powder product; (3) in the presence of air, described powder product in 100-1000 ℃ of roasting 0.5-36 hour, is obtained the invention provides catalyst; Wherein, it is 1 that the described consumption that contains aluminium salt and contain cobalt salt makes the cobalt in the final catalyst and the mole atomic ratio of aluminium:＞3-60, it is 1 that the consumption of described organic cosolvent makes cobalt and aluminium mole atomicity sum and the ratio of the molal quantity of cosolvent: 0.1-10, described cosolvent are selected from one or more in organic amine, organic acid, the organic hydrazine.
Compare with the catalyst that prior art provides, the invention provides catalyst and when keeping high reaction activity and high, have better C
5 +Selectivity.
The specific embodiment
According to catalyst provided by the invention, the mole atomic ratio of described cobalt and aluminium is preferably 1: 3.5-20, the RT value of described cobalt metal component is preferably 420 ℃-900 ℃.Described RT value is for adopting temperature programmed reduction (TPR) when catalyst is characterized, the summit temperature of the first reduction spectrum peak correspondence in the reduction spectrogram of the cobalt that exists with the oxidation state form.The RT value adopts on the Micromatics absorption instrument and measures.Concrete grammar is that 200 milligrams of 40-60 order particulate samples are placed sample cell, is warming up to 1000 ℃ under the Ar air-flow, and heating rate is 10 ℃/min, and reducing gas is formed 10%H
2/ N
2(vol.), flow is 50ml/min, and thermal conductivity detector (TCD) (TCD) detects and logging program heating reduction (TPR) spectrogram.
The cobalt of described effective dose is the customary amount that is used for the synthetic cobalt-base catalyst of Fischer-Tropsch, is benchmark in oxide and with the total amount of catalyst, is preferably 2.5-31 weight %, more preferably 5-31 weight %.
According to catalyst provided by the invention, aluminium oxide wherein is selected from amorphous alumina or has one or more mixture in the aluminium oxide of η, γ, θ, δ or α phase structure, is preferably amorphous alumina and/or gama-alumina.
According to catalyst provided by the invention, wherein can also contain one or more adjuvant components that cobalt-base catalyst performance is had modifying function known in the art.For example, be selected among Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Ce, Mn, Fe or the V one or more.In oxide and with the catalyst total amount is benchmark, and the content of described auxiliary agent is no more than 30 weight %, preferably is no more than 15 weight %.
According to method provided by the invention, when described catalyst adopted cobalt aluminate is mixed also roasting with aluminium oxide and/or aluminium oxide precursor method to prepare, wherein said cobalt aluminate can be commercially available commodity or adopt any one prior art for preparing.For example, disclosed a kind of nanometre grade cobalt aluminate of CN 1443811A and preparation method thereof, this cobalt aluminate are particularly suitable for being used for preparing catalyst provided by the invention, quote as a reference here.
Described aluminium oxide is selected from amorphous alumina or has one or more mixture in the aluminium oxide of η, γ, θ, δ or α phase structure, is preferably amorphous alumina and/or gama-alumina.
The precursor of described aluminium oxide is selected from one or more in various hydrated aluminas, the aluminium colloidal sol, preferred boehmite wherein.
The temperature of described roasting is 100 ℃-1000 ℃, is preferably 200-800 ℃, and roasting time is 0.5-36 hour, is preferably 1-12 hour.
Comprise when described catalyst adopts: (1) mixes, is dissolved into solution with at least a aluminum contained compound, at least a cobalt compound and at least a organic cosolvent with water; (2) described solution is heated to burning, burn off organic cosolvent under oxygen-containing atmosphere, obtains a kind of powder product; (3) in the presence of air, with described powder product when 100-1000 ℃ of roasting 0.5-36 hour method prepares, wherein, it is 1 that the described consumption that contains aluminium salt and contain cobalt salt makes the cobalt in the final catalyst and the mole atomic ratio of aluminium:＞3-60, it is 1 that the consumption of described organic cosolvent makes cobalt and aluminium atomicity sum and the ratio of the molal quantity of cosolvent: 0.1-10, be preferably 1: the described organic cosolvent of 0.2-5. (for example: urea is selected from organic amine, methylamine, ethamine), organic acid (for example: acetate, citric acid), organic hydrazine class (for example: oxalic acid two hydrazides, carbonohydrazides) one or more in. wherein said aluminum contained compound be selected from any water-soluble or in the presence of cosolvent water-soluble aluminum contained compound, preferred water-soluble inorganic salt containing aluminium wherein, as aluminum nitrate, aluminum sulfate, tri-chlorination chlorine, sodium metaaluminate etc. described cobalt compound be selected from any water-soluble or in the presence of cosolvent water-soluble cobalt compound, the preferred water-soluble cobalt inorganic salts that contain wherein are as cobalt nitrate, cobaltous sulfate, cobalt chloride, basic cobaltous carbonate etc.
Described solution is heated under oxygen-containing atmosphere, burns, and the method for burn off organic cosolvent has been carried out comparatively detailed description for adopting the conventional process of low-temperature burning synthetic technology synthesizing superfine powder about this method in CN 1443811A, do not give unnecessary details here.
For the mole atomic ratio by directly synthetic cobalt that obtains of the inventive method and aluminium is 1:＞3-60 catalyst can also comprise that optionally one is mixed the also step of roasting with it with aluminium oxide and/or aluminium oxide precursor.Wherein, to make the mole atomic ratio of cobalt and aluminium in the final catalyst be 1 to the consumption of each component:＞3-60, described sintering temperature are 100 ℃-1000 ℃, and roasting time is 0.5-36 hour.
In described catalyst, also contain one or more adjuvant components known in the art, as when containing one or more adjuvant components that are selected among Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Ce, Mn, Fe or the V, described Preparation of catalysts method also is included in the step of introducing described adjuvant component in the catalyst.For the introducing method of described auxiliary agent, the present invention is not particularly limited, preferable methods can be will contain the solution of described adjuvant component directly prepare with cobalt aluminate mixes also roasting with aluminium oxide and/or aluminium oxide precursor method; Also can be when the mixed solution of preparation described at least a aluminum contained compound, at least a cobalt compound and at least a organic cosolvent and water, directly will contain the method introducing that the compound of described adjuvant component mixes with this solution.In oxide and with the catalyst total amount is benchmark, and the described consumption that contains auxiliary compound should make the content of auxiliary agent in the final catalyst be no more than 30 weight %, preferably is no more than 15 weight %.
According to the invention provides catalyst, look different the article shaped that require can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding according to a conventional method, as the preparation of the method for extruded moulding.When adopting the method moulding of extrusion molding, can add an amount of extrusion aid and/or adhesive, extrusion molding then.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.
According to the invention provides catalyst, need be in the presence of hydrogen before being used for Fischer-Tropsch synthesis, the cobalt of oxidation state is carried out reduction activation, reducing condition is: reduction temperature is 200 ℃ to 1000 ℃, be preferably 400 ℃ to 800 ℃, recovery time is 1-96 hour, is preferably 2-24 hour, and described reduction can be carried out in pure hydrogen, also can in hydrogen and indifferent gas gaseous mixture, carry out, as carrying out in the gaseous mixture of hydrogen and nitrogen, Hydrogen Vapor Pressure is the 0.1-4 MPa, is preferably the 0.1-2 MPa.
The invention provides catalyst activity height, C
5 +Selectivity is good, be particularly suitable for in producing, heavy paraffins is the Fischer-Tropsch synthesis of purpose.
The following examples will the invention will be further described, but not thereby limiting the invention.
Embodiment 1
The present embodiment explanation the invention provides Catalysts and its preparation method.
Cabaltous nitrate hexahydrates, 131.2 gram ANN aluminium nitrate nonahydrates and the 67.5 gram urea of 29.1 grams are dissolved in 200 ml deionized water (cobalt and aluminium atomicity sum are 1: 2.5 with the ratio of the molal quantity of cosolvent), this solution placed be heated to catching fire in the muffle furnace, obtain fluffy foam-like powder material behind the organic cosolvent burn off, then under 500 ℃ and air existence condition, this powder material is continued roasting 3 hours in muffle furnace, obtain catalyst C1, the RT value of C1 and composition are listed in the table 1.
Embodiment 2
The present embodiment explanation the invention provides Catalysts and its preparation method.
Cabaltous nitrate hexahydrates, 225 gram ANN aluminium nitrate nonahydrates and the 105 gram urea of 29.1 grams are dissolved in 300 ml deionized water (cobalt and aluminium atomicity sum are 1: 2.5 with the ratio of the molal quantity of cosolvent), this solution placed be heated to catching fire in the muffle furnace, obtain fluffy foam-like powder material behind the organic cosolvent burn off, under 500 ℃ and air existence condition, this powder material is continued roasting 3 hours in muffle furnace, obtain catalyst C2, the RT value of C2 and composition are listed in the table 1.
Embodiment 3
The present embodiment explanation the invention provides Catalysts and its preparation method.
Cabaltous nitrate hexahydrates, 337.5 gram ANN aluminium nitrate nonahydrates and the 150 gram urea of 29.1 grams are dissolved in 500 ml deionized water (cobalt and aluminium atomicity sum are 1: 2.5 with the ratio of the molal quantity of cosolvent), this solution placed be heated to catching fire in the muffle furnace, obtain fluffy foam-like powder material behind the organic cosolvent burn off, under 500 ℃ and air existence condition, this powder material is continued roasting 3 hours in muffle furnace, obtain catalyst C3, the RT value of C3 and composition are listed in the table 1.
Embodiment 4
The present embodiment explanation the invention provides Catalysts and its preparation method.
Cabaltous nitrate hexahydrates, 131.2 gram ANN aluminium nitrate nonahydrates and the 70 gram citric acids of 29.1 grams are dissolved in 200 ml deionized water (cobalt and aluminium atomicity sum are 1: 0.8 with the ratio of the molal quantity of cosolvent), this solution placed be heated to catching fire in the muffle furnace, obtain fluffy foam-like powder material behind the organic cosolvent burn off, under 500 ℃ and air existence condition, this powder material is continued roasting 3 hours in muffle furnace, obtain catalyst C4, the RT value of C4 and composition are listed in the table 1.
Embodiment 5
The present embodiment explanation the invention provides Catalysts and its preparation method.
Cabaltous nitrate hexahydrates, 131.2 gram ANN aluminium nitrate nonahydrates and the 70 gram carbonohydrazides of 29.1 grams are dissolved in 200 ml deionized water (cobalt and aluminium atomicity sum are 1: 1.7 with the ratio of the molal quantity of cosolvent), this solution placed be heated to catching fire in the muffle furnace, obtain fluffy foam-like powder material behind the organic cosolvent burn off, under 500 ℃ and air existence condition, this powder material is continued roasting 3 hours in muffle furnace, obtain catalyst C5, the RT value of C5 and composition are listed in the table 1.
Embodiment 6
The present embodiment explanation the invention provides Catalysts and its preparation method.
With the cabaltous nitrate hexahydrate of 29.1 grams, the potassium nitrate (KNO of 1.01 grams
3), 131.2 the ANN aluminium nitrate nonahydrate of gram and 70 gram urea are dissolved in 200 ml deionized water (cobalt and aluminium atomicity sum are 1: 2.5 with the ratio of the molal quantity of cosolvent), this solution placed be heated to catching fire in the muffle furnace, obtain fluffy foam-like powder material behind the organic cosolvent burn off, under 300 ℃ and air existence condition, this powder material is continued roasting 3 hours in muffle furnace, obtain catalyst C6, the RT value of C6 and composition are listed in the table 1.
Embodiment 7
The present embodiment explanation the invention provides Catalysts and its preparation method.
Ammonium molybdates, 131.2 gram ANN aluminium nitrate nonahydrates and the 70 gram urea of the cabaltous nitrate hexahydrates of 29.1 grams, 6.64 grams are dissolved in 200 ml deionized water (cobalt and aluminium atomicity sum are 1: 2.5 with the ratio of the molal quantity of cosolvent), this solution placed be heated to catching fire in the muffle furnace, obtain fluffy foam-like powder material behind the organic cosolvent burn off, under 700 ℃ and air existence condition, this powder material is continued roasting 3 hours in muffle furnace, obtain catalyst C7, the RT value of C7 and composition are listed in the table 1.
Comparative Examples 1
This Comparative Examples explanation reference catalyst and preparation method thereof.
According to US 6,586, the preparation method of catalyst B prepares catalyst D1 in 481, the RT value of D1 and form and list in the table 1.
Comparative Examples 2
Get 600 ℃ of 50.00g alumina powders (Shandong Aluminum Plant) after the roasting, take by weighing 116.3 gram cabaltous nitrate hexahydrates, according to the volume obtain solution of saturated dipping, with this solution impregnation aluminium oxide, left standstill 8 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings made catalyst in 4 hours in muffle furnace then.Catalyst is designated as D2.
Table 1
| Embodiment | The catalyst precursor thing | Cobalt oxide weight % | Auxiliary agent (oxide meter) weight % | RT ℃ | Cobalt/aluminium (mol ratio) |
| 1 | C1 | 30.9 | 0 | 455 | 1∶3.5 |
| 2 | C2 | 20.7 | 0 | 471 | 1∶6.0 |
| 3 | C3 | 14.8 | 0 | 483 | 1∶9.0 |
| 4 | C4 | 30.9 | 0 | 453 | 1∶3.5 |
| 5 | C5 | 30.9 | 0 | 460 | 1∶3.5 |
| 6 | C6 | 30.4 | 1.7 | 452 | 1∶3.5 |
| 7 | C7 | 29.3 | 5.3 | 490 | 1∶3.5 |
| Comparative Examples 1 | D1 | 14.7 | 0 | 362 | 1∶9.0 |
| Comparative Examples 2 | D2 | 30.9 | 0 | 325 | 1∶3.5 |
Embodiment 8
The present embodiment explanation the invention provides the performance of catalyst.
Catalyst reduction: C1 places quartz tube reactor with catalyst, feeds hydrogen and is warming up to 600 ℃ with 5 ℃/minute heating rate, reduces 5 hours, hydrogen-pressure 0.1 MPa, hydrogen flowing quantity is 100ml/min (status of criterion), naturally cools to room temperature, the catalyst after obtaining reducing.
Evaluating catalyst: the catalyst C1 after liquid saualane 70g and the reduction is placed 0.5 liter tank reactor.Be warming up to 220 ℃ under reaction pressure 2.5MPa, stirring, regulating the synthesis gas flow is 100ml/min (status of criterion) reaction.Synthesis gas is formed H
2/ CO/N
2=64/32/4.React and get gas phase, liquid phase and kettle base solution respectively after 30 hours and analyze.Wherein, the gas phase sample adopts triple channel gas chromatographic analysis H
2, CO, CO
2, N
2, CH
4, C2, C3, C4, C5 content, calculate the conversion ratio (X of CO
CO, %) and CO
2Selectivity (S
CO2, %), CH
4Selectivity (S
CH4, %) and C
5 +Selectivity (S
C5+, %).The results are shown in table 2.
Embodiment 9
The present embodiment explanation the invention provides the performance of catalyst.
Sample thief C2, other adopts and embodiment 8 identical condition evaluating catalyst C2.The results are shown in table 2.
Embodiment 10
The present embodiment explanation the invention provides the performance of catalyst.
Sample thief C3 adopts and embodiment 8 identical condition evaluating catalyst C3, the results are shown in table 2.
Comparative Examples 3
The performance of this Comparative Examples explanation reference catalyst.
Sample thief D1 adopts and embodiment 8 identical condition evaluating catalyst D1.The results are shown in table 2.
Comparative Examples 4
The performance of this Comparative Examples explanation reference catalyst.
Sample thief D2 adopts and embodiment 8 identical condition evaluating catalyst D2.The results are shown in table 2.
Table 2
| Example | Catalyst | X CO，％ | S CO2，％ | S CH4，％ | S C5+，％ |
| 8 | C1 | 54.5 | 1.86 | 5.74 | 87.2 |
| 9 | C2 | 46.8 | 2.02 | 5.54 | 87.4 |
| 10 | C3 | 38.7 | 1.78 | 5.66 | 87.1 |
| Contrast 3 | D1 | 34.9 | 2.85 | 10.86 | 80.7 |
| Contrast 4 | D2 | 32.2 | 2.96 | 12.36 | 76.5 |
Result in the table 2 shows, the invention provides catalyst carbon monoxide conversion ratio height, and the activity of such catalysts height is described, has higher C simultaneously
5 +Hydrocarbon selective, and methane and CO
2Selectivity low.
Claims (12)
1. Co based Fischer-Tropsch synthesis catalyst contains the cobalt metal component and the aluminium oxide of effective dose, and the mole atomic ratio of cobalt wherein and aluminium is 1:＞3-60, and the RT value of described cobalt metal component is 400 ℃ to 1000 ℃; When described RT value characterizes catalyst for adopting temperature programmed reduction, the summit temperature of the first reduction spectrum peak correspondence in the reduction spectrogram of the cobalt that exists with the oxidation state form, the RT value is for adopting Micromatics absorption instrument, 200 milligrams of 40-60 order particulate samples are placed sample cell, under the Ar air-flow, be warming up to 1000 ℃, heating rate is 10 ℃/min, and reducing gas is formed 10%H
2/ N
2(vol.), flow is 50ml/min, the summit temperature of the first reduction spectrum peak correspondence in thermal conductivity detector (TCD) detection and the logging program heating reduction spectrogram.
2. catalyst according to claim 1 is characterized in that, the mole atomic ratio of described cobalt and aluminium is 1: 3.5-30, described cobalt metal component RT value is 420 ℃-900 ℃.
3. catalyst according to claim 1 is characterized in that, is benchmark in oxide and with the total amount of catalyst, and the content of cobalt is 2.5-31 weight % in the described catalyst.
4. catalyst according to claim 3 is characterized in that, is benchmark in oxide and with the total amount of catalyst, and the content of cobalt is 5-31 weight % in the described catalyst.
5. catalyst according to claim 1 is characterized in that described aluminium oxide is selected from amorphous alumina and gama-alumina.
6. according to any described catalyst of claim 1-5, it is characterized in that, described catalyst also contains one or more promoter metal components that are selected among Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Mn, Fe or the V, in oxide and with the catalyst total amount is benchmark, and described promoter metal components contents is no more than 30 weight %.
7. the described Preparation of catalysts method of claim 1, comprise cobalt aluminate is mixed with aluminium oxide and/or aluminium oxide precursor and roasting, it is 1 that the consumption of each component makes the mole atomic ratio of cobalt and aluminium in the final catalyst:＞3-60, described sintering temperature is 100 ℃-1000 ℃, and roasting time is 0.5-36 hour.
8. method according to claim 7 is characterized in that, described sintering temperature is 200 ℃-800 ℃, and roasting time is 1-12 hour.
9. method according to claim 7, it is characterized in that, described method also is included in and introduces adjuvant component in the catalyst, described adjuvant component is selected from one or more among Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Mn, Fe or the V, in oxide and with the catalyst total amount is benchmark, and the introducing amount of described promoter metal component is no more than 30 weight %.
10. the described Preparation of catalysts method of claim 1, comprising: (1) mixes, is dissolved into solution with at least a aluminum contained compound, at least a cobalt compound and at least a organic cosolvent with water;
(2) described solution is heated to burning, burn off organic cosolvent under oxygen-containing atmosphere, obtains a kind of powder product; (3) in the presence of air, described powder product in 100-1000 ℃ of roasting 0.5-36 hour, is obtained described catalyst; Wherein, it is 1 that the consumption of described aluminum contained compound and cobalt compound makes the mole atomic ratio of cobalt in the final catalyst and aluminium:＞3-60, it is 1 that the consumption of described organic cosolvent makes cobalt and aluminium atomicity sum and the ratio of the molal quantity of cosolvent: 0.1-10, described cosolvent are selected from one or more in organic amine, organic acid, the organic hydrazine.
11. method according to claim 10 is characterized in that, the temperature of described roasting is 200 ℃-800 ℃, and roasting time is 1-12 hour, and it is 1 that the consumption of described organic cosolvent makes cobalt and aluminium atomicity sum and the ratio of the molal quantity of cosolvent: 0.2-5.
12. method according to claim 10, it is characterized in that, described method also is included in and introduces adjuvant component in the catalyst, described adjuvant component is selected from one or more among Li, Na, K, Mg, Ca, Sr, Cu, Mo, Ta, W, Ru, Zr, Ti, REO, Re, Hf, Mn, Fe or the V, in oxide and with the catalyst total amount is benchmark, and the introducing amount of described promoter metal component is no more than 30 weight %.
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| CN108043421A (en) * | 2017-12-13 | 2018-05-18 | 太原理工大学 | A kind of preparation method of the nanometer cobalt-manganese catalyst of synthesis gas conversion preparing low carbon hydrocarbons |
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| CN102233273B (en) * | 2010-04-30 | 2013-03-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and application thereof |
| CN102233268B (en) * | 2010-04-30 | 2013-06-26 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and application thereof |
| CN102441402B (en) * | 2010-10-12 | 2013-11-06 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis catalyst and application thereof |
| CN102441352B (en) * | 2010-10-12 | 2014-01-01 | 中国石油化工股份有限公司 | Method for synthesizing Fischer Tropsch of slurry bed |
| CN106867561A (en) * | 2017-03-07 | 2017-06-20 | 北京神雾环境能源科技集团股份有限公司 | The method of F- T synthesis diesel oil distillate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367814A (en) * | 1998-05-27 | 2002-09-04 | 能源国际有限公司 | Improved fischer-tropsch activity for 'Non-Promoted' cobalt-on-alumina catalysts |
-
2005
- 2005-12-14 CN CN200510130076A patent/CN1981927B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1367814A (en) * | 1998-05-27 | 2002-09-04 | 能源国际有限公司 | Improved fischer-tropsch activity for 'Non-Promoted' cobalt-on-alumina catalysts |
Non-Patent Citations (2)
| Title |
|---|
| 代小平 等.钴负载量和焙烧温度对F2T合成用Co/ Al2O3 催化剂活性的影响.催化学报21 2.2000,21(2),161-164. |
| 代小平 等.钴负载量和焙烧温度对F2T合成用Co/ Al2O3 催化剂活性的影响.催化学报21 2.2000,21(2),161-164. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108043421A (en) * | 2017-12-13 | 2018-05-18 | 太原理工大学 | A kind of preparation method of the nanometer cobalt-manganese catalyst of synthesis gas conversion preparing low carbon hydrocarbons |
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